Silver halide emulsion layers containing yellow dye forming couplers



United States Patent 3,408,194 SILVER HALIDE EMULSION LAYERS CONTAIN-ING YELLOW DYE FORMING COUPLERS Anthony Loria, Rochester, N.Y., assignorto Eastman Kodak Company, Rochester, N.Y., a corporation of New JerseyNo Drawing. Continuation-impart of application Ser. No. 312,894, Oct. 1,1963. This application July 6, 1965, Ser. No. 469,887

9 Claims. (Cl. 96100) ABSTRACT OF THE DISCLOSURE Open chain reactivemethylene two-equivalent yellowforming couplers in which one of thehydrogen atoms of the active methylene group is replaced with a cyclooxygroup are used to advantage in color developer solutions and inlight-sensitive photographic emulsion layers for forming yellow dyeimages in color photography.

This is a continuation-impart application of Loria US. application Ser.No. 312,894, filed Oct. 1, 1963 now abandoned.

This invention relates to photography and particularly to a new class oftwo-equivalent dye-forming couplers and their use in color photography.

The formation of colored photographic images by the coupling of oxidizedaromatic primary amino developing agents with color-forming or couplingcompounds is well known. In these processes the subtractive process ofcolor formation is ordinarily used and the image dyes are intended to becyan, magenta, and yellow, the' colors that are complementary to theprimary colors. Usually phenol or naphthol couplers are used to form thecyan dye imag pyrazolone or 2-(alpha-cyanoacetyl)-coumarone couplers areused to form the magenta dye image, and open-chain reactive methylenecouplers having two carbonyl groups attached to the active methylenegroup are used to form the yellow dye image.

In these color developing processes the color forming coupler may beeither in the developer solution or incorporated in the light-sensitivephotographic emulsion layer so that during development it is availablein the emulsion layer to react with the color developing agent that isoxidized by silver image development. Ditfusable type couplers are usedin color developer solutions. Fischer type couplers and nondiffusingcouplers are incorporated in photographic emulsion layers. When the dyeimage formed is to be used in situ, couplers are selected which formnonditlusing dyes. The dye image used for image transfer processesshould be diffusable but capable of being mordanted or fixed in areceiving layer. For this purpose a coupler is selected which willproduce this type of dye.

Conventional color-forming couplers are four-equivalent, that is, theyrequire the development of four molecules of silver halide in order tosupply one molecule of oxidized color developing agent that is free tocouple and form one molecule of dye. Two-equivalent couplers require thedevelopment of only two molecules of silver halide to bring about theformation of one molecule of dye. Two-equivalent couplers are verydesirable for color photography, since only one-half the usual amount ofsilver halide is needed and the light-sensitive coatings can thus bemade thinner. Certain of the available twoequivalent couplers tend toproduce more stain than is ice desired from coupling in areas of thecolor photographic element being developed where the silver halidegrains had not been exposed, and others do not have the desired couplingreactivity, especially for incorporation in photographic emulsion layersat low coupler solvent ratios. Other characteristics required ofcouplers, that are not always exhibited by other classes of couplers tothe desired degree, are low printout, and low yellowing in emulsionlayers containing them. Furthermore, the dyes formed from other classesof couplers do not always have the desired spectral absorptioncharacteristics, light fading and low heat fading properties.

It is therefore an object of my invention to provide a new class ofcolorless two-equivalent dye-forming couplers which have a high degreeof reactivity but which do not produce stains caused by nonimage-formingcoupling that is a problem with some of the prior art two-equivalentdyeforming couplers.

Another object of my invention is to provide valuable cyclooxysubstituted two-equivalent couplers for forming dye images that havegood spectral absorption characteristics, and good stability toprolonged exposure to light, heat and high humidity.

Another object is to provide cyclooxy substituted twoequivalent couplerswhich have good coupling reactivity and which include the diffusibletype coupler, the Fischer type and the nondifiusing type couplers whichare readily incorporated in light-sensitive hydrophilic colloid-silverhalide emulsion layers in a Wide range of coupler to solvent ratios.

Still another object is to provide photographic hydrophiliccolloid-silver halide emulsion layers containing my cyclooxy substitutedtwo-equivalent dye-forming couplers.

Still further objects will be apparent from the following specificationand claims.

These and other objects are accomplished according to my invention bythe preparation and use of my novel class of couplers. The couplers ofmy invention are open-chain reactive methylene two-equivalent couplerswherein one of the hydrogens of the active methylene group is replacedwith a cyclooxy substituent; the cyclooxy group includes, for example,unsubstituted aryloxy, substituted aryloxy, e.g., arylenedioxy, as wellas the unsaturated and saturated heterocyclooxy groups such as4-pyridyloxy and tetrahydropyranyloxy, respectively. My two-equivalentcouplers are derived to advantage from any of the known fourequipalentopen-chain types, e.g., the alpha-acylacetamides. the2-(alpha-cyanoacetyl) coumarones and the alpha-acylacetonitriles, etc.The effectiveness of my couplers as two-equivalent couplers is notdependent on the specific composition of the coupler moiety, and it willbe understood that this moiety may be varied widely to meet suchrequirements as spectral absorptivity, reactivity, solubility, andditfusibility, as may be imposed by the photographic system in which thecoupler should be used. Typical examples of different classes ofcouplers which are in cluded in my invention are alpha-acylacetamides,2-(alpha-cyanoacetyl)coumarones, and alpha-acylacetonitriles,

etc.

Included among the couplers of my invention are those represented toadvantage by the following formula:

wherein R represents an alkyl radical, either straight or branched chainof from 1 to 30 carbon atoms, a monoor bicyclic alkyl radical such ascyclohexyl, terpenyl, e.g., a norbony-l radical, etc., the said R groupmay also represent a substituted alkyl radical containing substituentgroups such as halogen, nitro, hydroxyl, carboxyl, amino, substitutedamino (N-alkylamino, N,N-dialkylamino, anilino, N-alkylanilino, etc.), acarboxyl ester (e.g. carboalkoxy, carbophenoxy, etc.), sulfo, a sulfoester (e.g., methoxysulfonyl, butoxysulfonyl, phenoxysulfonyl, etc.),an'amido group (e.g., an acetamido, a butyramido, ethylsulfonamido,etc.), a carbamyl group (e.g., carbamyl, an N-alkylcarbamyl group, anN-phenylcarbamyl group, etc.), a sulfamyl group (e.g., sulfarnyl,N-alkylsulfamyl, N,N-dialkylsulfamyl, N-phenylsulfamy, etc.), an alkoxygroup, an aryl group, an aryloxy group, an alkylsulfonyl group, anarylsulfonyl group, etc., the said R group also represents an aryl group(e.g., phenyl naphthyl, etc.) including substituted aryl groups wherethe substituents may be any of those that are defined previously for Rwhen substituted alkyl, the said R group also represents a hcterocyclicgroup (e.g., furanyl, benzofuranyl, benzothiazolyl, oxazolyl,imidazolyl, quinolinyl, etc.) each of which heterocyclic groups may besubstituted with groups such as previously defined for the substitutedalkyl groups; R' represents a carbamyl group (e.g., an unsubstitutedcarbamyl, an alkylcarbamyl group in which the alkyl group is eitherstraight or branched chain having from 1 to 30 carbon atoms, a mono orbicyclic group such as cyclohexyl, terpenyl, e.g., a norbornyl group,etc., a dialkylcarbamyl group in which a combination of any two of theabove mentioned alkyl groups are substituted on the nitrogen atom of thecarbamyl group, an arylcarbamyl group in which the aryl group is a groupsuch as phenyl, naphthyl, etc., an aralkylcarbamyl group in which acombination of any two of the above alkyl and aryl groups aresubstituted on the nitrogen atom of the carbamyl group, e.g., anN-methyl-N-phenylcarbamyl group, an N-butyl-N-tolylcarbamyl group, etc.,a 'heterocyclic carbamyl group in which the heterocyclic group is agroup such as a thiazolyl group, a benzothiazolyl group, anaphthothiazolyl group, an oxazolyl group, a pyridinyl group, aquinolinyl group, an alkyl heterocyclic carbamyl group in which acombination of any two of the above alkyl groups and heterocyclicgroups, respectively, are substituted on the nitrogen atom of thecarbamyl group, e.g., an N-(Z-benzothiazolyl)-N-methylcarbamy1 group,etc., an N-aryl-N-heterocyclic carbamyl group in which a combination ofany two of the above aryl groups and heterocyclic groups, respectively,are substituted on the nitrogen atom of the carbamyl group (e.g., anN-phenyl- N-(Z-thiazolyl) carbamyl group, etc.), the said alkyl, aryl,and heterocyclic groups on the carbamyl groups (R') may containsubstituent groups such as defined for substituted alkyl in R above, theR group may also represent the cyanotgroup; n is an integer of from 1 to2; R represent the cyano group such as phenyl, naphthyl, etc., aheterocyclic group (such as a 4-pyridinyl group, a Z-tetrahydropyranylgroup, a 2-(1,2,3,4)-tetrahydroquinolinyl group, etc.) when n representsthe integer l, and R represents a divalent cyclo group (such as arylene,e.g. 1,3- phenylene, 1,4-phenylene, 1,4-naphthylene, 2,5-pyridyl, etc.),the said cyclo groups may contain substituent groups such as defined forsubstituted alkyl in R above.

My two-equivalent couplers are characterized by having a cyclooxy groupon the coupling position of the coupler which gives them good couplingreactivity and other valuable properties. Non-image-forming butstainproducing reactions characteristic of certain prior arttwo-equivalent dye-forming couplers are not exhibited by my couplers.Some of my non-ditfusible couplers have good coupling reactivity whenincorporated in emulsion layers with no high-boiling coupler solvents,while others are dispersed to advantage in high-boiling solventsolutions in a wide range of coupler to solvent ratios.

,4 Included among mynovel couplers are the following typical exampleswhich are used to illustrate but not limit my invention. 1Alpha-(4-nitro-3-pentadecylphenoxy)-alpha1-pivaly1-4-sulfamylacetanilide (2) Alpha- (4-palmitamidophenoxy) -alpha-pivalyl-4-sulfamylacetanilide I IH CmHal (3 A1pha-(4-nitro-3 -pentadecylphenoxy)-alpha-pivalyl- 2-chloro-4-sulfamylacetanilide (4) Alpha- [4-(N-methyl-N-octadecylsulfamyl) phenoxy] -alpha-pivaly1-4-sulfamylacetanilide 10? Alph a- 4-acetylphenoxy) -alpha-{ 3- [7- (2,4-

dl-tert-amylphenoxy) -butyramido]-benzoyl}-2- methoxyacetanilide I (l 1)Al pha-{3- ['y- 2,4-di-tert-amylphenoxy b utyramido] benzoyl}-alpha-(4-sulfamylphenoxy) -2-methoxyacetanilide 12) A'lpha-{3-[alpha-(2,4-di-tert-amylphenoxy) acetanndo] benzoyl}-alpha- (4-phenylphenoxy)-2- methoxyacetanilide I T ll I nHw ILIO: (41) Alpha- 2-naphthoyl)-alpha-phenoxyacetonitrile onmoooono ONH-S02N (I) CJBHU SO3Na CHsCONHSOaNa (43 Alpha-benzoyl-alpha- 4-pyridinyloxy) acetanilide (3,1150 o([3110 ONHCsH (44) Alpha-benzoyl-alpha-[4-(N,N-dimethylsulfamyl)phenoxy] -2-decyloxyacetanilide The ditfusible couplers of my invention,such as couplers through 21 and 39, 41, and 43 are used to advantage incolor developer solutions used to color develop lightsensitve elementsused for color photography which do not contain the color-formingcoupler. Any of the well known primary aromatic amino color-formingsilver halide developing agents such as the phenylenedia'mines, e.g.,diethyl-p-phenylenediamine hydrochloride, monomethyl-pphenylenediaminehydrochloride, dimethyl-p-phenylenediamine hydrochloride,2-amino-5-diethylaminotoluene hydrochloride,2-amino-5-(N-ethyl-N-laurylamino)-toluene, N ethyl N (betamethanesulfonamidoethyl) 3- methyl-4-aminoaniline sulfate,N-ethyl-N-(beta-methanesulfonamidoethyl) 4 aininoaniline,4-[N-ethyl-N-(betahydroxyethyl)amine]aniline, etc., the p-aminophenolsand their substitution products where the amino group is unsubstitutedmay be used in the alkaline developer solution with my couplers. Variousother materials may be included in the developer solutions dependingupon the particular requirements, for example, an alkali metal sulfite,carbonate, bisulfite, bromide, iodide, etc., and the thickening agentsused in 'viscous developer compositions, such as, carboxymethylcellulose, carboxyethyl cellulose, gelatin, etc. The following isatypical developer solution given to illustrate but not limit theinvention.

Z-amino-S-diethylaminotoluene HCl g Sodium sul'fite (anhydrous) g a 2.0Sodium carbonate (anhydrous) g 20.0 Potassium bromide g 1.0 Coupler g2.0

Water to ml 1000.0

The other coupler examples used to illustrate my invention arenondiifusing and are used to advantagein photographic emulsion layers.Couplers such as 22, 23, 27, 30, 32, 34, and 42 illustrate those thatare incorporated as Fischer type couplers. The other nondilfusingcouplers, e.g., 1 through 14, 24, 25, 26, 28, 29, 31, 33, 35, 36, 37,38, 40, are incorporated inemulsion layers by methods such as aredescribed by Mannes et al., US. Patent No. 2,304,939, issued Dec. .15,19 42, Jelley et al., US. Patent 2,322,027, isued June 15, 1943, etc.,in which highboiling organic solvents are used to dissolve the coupler,and by methods described in Vittu'm et al., US. Patent 2,801,170 andFierke et al., US. Patent No. 2,801,- 171, both issued July 30, 1957 andJulian, US. Patent No. 2,949,360, issued Aug. 16, 1960 in whichlow-boiling or water-soluble organic solvents are used with or in placeof the high-boiling solvent. Not only can emulsion layers containing mycouplers be made thinner because they require only one-half the silverhalide required by conventional couplers (i.e., four-equivalentcouplers) but some of my couplers are sufliciently reactive that they donot require any high-boiling coupler solvent that is usually required bycouplers. Thin image-forming layers are very desirable because theycause less light scattering and produce sharper images.

My nonditfusing couplers 1, 2, 3 and 4 each have a sulfamyl group (on anoncoupling position) which ionizes and forms a difiusible dye uponcolor development at a pH above 12.

The other nonditfusing couplers 5 through 14, 24, 25 and 44 used toillustrate my invention form nondifiusing dyes and are used to advantagein any photographic element where incorporated image-forming couplersare desired. Couplers l, 2, 3 and 4 when developed with a colordeveloper with a pH lower than 12 will produce nondiifusing dye images.

Coupler 42 contains a preformed dye attached to the coupler on thearyloxy group. This dye i eliminated on the coupling of the coupler withoxidized color devel oper and diffuses out of the film. This coupler canbe used as a magenta colored coupler for the purpose of correcting forthe unwanted blue absorption of yellow image dyes, i.e., that formedfrom the coupler itself as Well as that formed from other yellowcouplers. Generally, such a coupler as this would be used in combinationwith another image-forming yellow coupler in the same layer.

My couplers are used in the color development of photographichydrophilic colloid-silver halide emulsion layers of the developing-outtype either in the color developer solution or in the emulsion layer.The emulsions may contain silverchloride, silver bromide, silver iodide,silver chlorobromide, silver bromoiodide, silver chlorobromoiodide,etc., as the light-sensitive material.

Hydrophilic colloids used to advantage include gelatin, colloidalalbumin, a cellulose derivative, or a synthetic resin, for instance, apolyvinyl compound. Some colloids which may be used are polyvinylalcohol or a hydrolyzed polyvinyl acetate described in Lowe, US. Patent2,286,-

215, issued June 16, 1942; a far hydrolyzed cellulose ester, such ascellulose acetate hydrolyzed to an acetyl content of 1926% as describedin Lowe et al., U.S. Patent 2,327,808, issued Aug. 24, 1943; awater-soluble ethanolamine cellulose acetate as described in Yutzy, U.S.Patent 2,322,085, issued June 15, 1943; a polyacrylamide having acombined acrylamide content of 30-60% and a specific viscosity of0.251.5 on an imidized polyacrylamide of like acrylamide content andviscosity as described in Lowe et al., U.S. Patent 2,541,474, issuedFeb. 13, 1951; zein as described in Lowe, U.S. Patent 2,563,- 791,issued Aug. 7, 1951, a vinyl alcohol polymer containing urethanecarboxylic acid groups of the type described in Unruh et al., US. Patent2,768,154, issued Oct. 23, 1956, or containing cyano-acetyl groups, suchas the vinyl alcohol-vinyl cyano-acetate copolymer as described in Unruhet al., U.S. Patent 2,808,331, issued Oct. 1, 1957; or a polymericmaterial which results from polymerizing a protein or a saturatedacylated protein with a monomer having a vinyl group as described inIllings- Worth et al., U.S. Patent 2,852,382, issued Sept. 16, 1958.

The emulsions used in the photographic element of my invention can bechemically sensitized by any of the accepted procedures. The emulsionscan be digested with naturally active gelatin, or sulfur compounds canbe added, such as those described in Sheppard, U.S. Patent 1,574,944,issued Mar. 2, 1926; Sheppard et al., U.S. Patent 1,623,499, issued Apr.5, 1927; and Sheppard et al., U.S. Patent 2,410,689, issued Nov. 5,1946.

The emulsions can also be treated with salts of the noble metals, suchas ruthenium, rhodium, palladium, iridium and platinum, as described inSmith et al., U.S. Patent 2,448,060, issued Aug. 31, 1948 and asdescribed in Trivelli et al., U.S. Patents 2,566,245 and 2,566,263, bothissued Aug. 28, 1951.

The emulsions can also be optically sensitized with cyanine andmerocyanine dyes, such as those described in Brooker, U.S. Patents1,846,301 and 1,846,302, both issued Feb. 23, 1932; and 1,942,854,issued Ian. 9, 1934; White, U.S. Patent 1,990,507, issued Feb. 12, 1935;Brooker and White, U.S. Patents 2,112,140, issued Mar. 22, 1938;2,165,338, issued July 11, 1939; 2,493,747, issued Jan. 10, 1950; and2,739,964, issued Mar. 27, 1956; Brooker et al., U.S. Patent 2,493,748,issued Jan. 10, 1950; Sprague, U.S. Patents 2,503,776, issued Apr. 11,1950, and 2,519,001, issued Aug. 15, 1950; Heseltine et al., U.S. Patent2,666,761, issued Jan. 19, 1954; Heseltine, U.S. Patent 2,734,900,issued Feb. 14, 1956; Van Lare, U.S. Patent 2,739,149, issued Mar. 20,1956; and Kodak Limited, British 450,958, accepted July 15, 1936.

The emulsions may also contain speed-increasing compounds of thequaternary ammonium type of Carroll, U.S. Patent 2,271,623, issued Feb.3, 1942; Carroll et al., U.S. Patent 2,288,226, issued June 30, 1942;and Carroll et al., U.S. Patent 2,334,864, issued Nov. 3, 1943; and thepolyethylene glycol type of Carroll et al., U.S. Patent 2,708,- 162,issued May 10, 1955.

The emulsions can also be chemically sensitized with gold salts asdescribed in Waller et al., U.S. Patent 2,399,,- 083, issued Apr. 23,1946 or stabilized with gold salts as described in Damschroder, U.S.Patent 2,597,856, issued May 27, 1952; and Yutzy et al., U.S. Patent2,597,- 915, issued May 27, 1942. Suitablecompounds are potassiumchloroaurite, potassium aurithiocyanate, potassium chloroaurate, aurictrichloride and 2-aurosulfobenzothiazole methochloride.

The couplers of my invention may also be used to advantage inimage-forming layers, either alone or with image-forming compounds otherthan silver halide, such as ZnO, ZnS, CdS, CdSe, NiS, etc., either Withor without binders such as gelatin, polyvinyl alcohol, etc.

The above-described emulsions can be coated on a wide variety ofphotographic emulsion supports. Typical supports include cellulosenitrate film, cellulose acetate film, polyvinyl acetal film, polystyrenefilm, polyethylene terephthalate film, polyethylene film, polypropylenefilm, and

-10 related films of resinous materials, as well as paper, glass andothers.

Usually my emulsions are coated on photographic supports in the form ofmultilayer color photographic elements wherein at least threedifferently sensitized emulsion layers are coated over one another onthe sup port. Usually the support is coated in succession with ared-sensitive layer, a green-sensitive layer and a bluesensitive layereither with or without a Carey Lea filter layer between theblue-sensitive and green-sensitive layers. The three differently colorsensitized layers may be arranged in any other order over one anotherthat is desirable; however, the Carey Lea filter layer obviously wouldnot be put over the blue-sensitive layer. 'Prefererably, theselight-sensitive layers are arranged on the same side of the support.

Elements made for image transfer processing may use a separate receptionsheet which is contacted with the light-sensitive layer during itsdevelopment or the reception layer may be an integral part of thelight-sensitive element. Any of the support materials mentionedpreviously may be used for a separate reception sheet. The receptionlayer comprises a hydrophilic colloid layer containing a cationicmordant, e.g., the polymers of amino guanidine derivatives of vinylmethyl ketone such as described in Minsk, U.S. Patent 2,882,156, grantedApr. 14, 1959. Other mordants include the 2-vinyl pyridine polymermetho-p-toluene sulfonate and similar com pounds described in Sprague etal. U.S. Patent 2,484,430, granted Oct. 11, 1949, and cetyl trimethylammonium bromide, etc. Particularly effective mordanting compositionsare described in copending applications of Kneckel et al., U.S. Ser. No.211,095, filed July 19, 1962, now U.S. Patent 3,271,148, and Bush, U.S.Ser. No. 211,094, filed July 19, 1962, now U.S. Patent 3,271,147.Additional variations of the image transfer elements and processes inwhich couplers of my invention (such as 1, 2, 3, 4, 22 and 23) can beused to advantage, are described in copending application of Whitmoreand Mader, U.S. Ser. No. 222,105, filed Sept. 7, 1962, now U.S. Patent3,227,550. H

My invention is still further illustrated by the following typicalexamples.

Example 1 Single layer gelatino-silver bromoiodide emulsions containingyellow-forming coupler and the coupler solvent di-n-butylphthalate weremade for my couplers 1, 2, 3, 4, 5, 11, 24 and 25. The amounts ofgelatin, silver bromoiodide, and coupler solvent used in the coatingsare listed in Table 1. The each instance the coupler was used so as tobe coated at 60 mg./ft.

Strips of the coatings were given identical exposures to a 0.3 neutraldensity step tablet in a 1B intensity scale sensitometer and processedthrough the following process:

Process steps: Time Water dip min 30 Development sec 10 Stop bath sec 5Ferricyanide bleach sec 5 Wash a sec 5 Fixing bath sec 5 Wash sec 10Photo-Flo (wetting agent solution) min 30 Dry.

The following developer solutions were used in this process:

Developer 1 Sodium sulfite g 2 2-amino-5-diethylamino-toluene I-ICl g 2Sodium carbonate g 20 Potassium bromide 'g 2 Water to l 1 Conventionalacid stop bath, potassium ferricyanide bleach, sodium thiosulfate fixingbaths were used in this process.

Spectrophotometric curves were made to determine the A and the D (at Afor the yellow dye images in each coating. Light fade, printout, heatfade and yellowing data' were also obtained for each processed coating.The fading measurements were made at an original dye density of about1.2 by determining the density decrease produced in thespectrophotometric curve by 30 hours exposure to a Xenon are (lightfade), and the density decrease produced in the spectrophotometric curveby storage in an oven at 140 F. at 70% RH for one week (heat fade). Theprintout values, that is, the percent change in transmission produced inan area of the processed element having no exposure by 30 hours exposureto a Xenon arc were determined for each coating. The yellowing values,that is, the percent decrease in trans mission produced in an unexposedarea of the processed element by storage at 140 F. and 70% RH for oneweek were determined for each coating. The data are listed in Table 1.

Y 12 and for a-benzoyl-2-methoxyacetanilide as a control. The alkalinecolor developer comprised:

Na SO g Diethyl-p-phenylenediamine hydrochloride g 3.0 Coupler m. 0.01Alkali (to give a pH of 11.5).

Waterto l 1.0

Stripsof a multilayer structure containing a layer of light-sensitivesilver halide emulsion were given sensitometric exposure with the 1Bsensitimeter mentioned in Example 1. These strips were given thefollowing processing steps: 1 minute, 5 seconds in a conventionalformalin-sodium bisulfide prehardener, water washed, 2 /2 minutesdevelopment in a conventional hydroquinone p-methylaminophenol sulfatedeveloper, water washed,

fogged, 5 minutes yellow color development, Water 'Washed,3 minutes ina'conventional potassium ferricyanide bleach bath, 2 minutes ofconventional sodium thiosulfate fixing, water washing and drying. TheAm, in m was measured at 'a density of 1 and the percent of yellow dyefading (at a density of 1) produced by exposure to tungsten light andstorage in an oven was determined for the processed strips. The resultsare summarized in Table 2.

TABLE 2 3 Day 2 Weeks Oven Fade Coupler Used in Am Tungsten at 70% RHand Color Developer in ma Fade (percent) 140 F. (percent) The resultsshow that my couplers produced good TABLE 1 Photographic Data SilverBromo- Ratio of Coupler Coating No. Gelatin, iodide, mgJlt. Coupler toCoupler Developer A... Dmnx. L ght Print Out, Heat Yellowmg,

rug/ft. No. Solvent Formula. in ma Fade Percent Fade Percent 250 100 21:1 1 451 1. 64 33 +4 13 5 250 100 4 1:1 1 452 2. 72 33 +6 08 3 250 1004 1:1 2 448 2. 60 14 +3 18 5 250 100 5 2: 1 1 451 1. 90 23 +8 08 2 250100 5 2:1 2 448 1. 74 10 +8 10 4 250 100 11 2: 1 1 447 3. 28 38 +1 02 6300 150 24 2:1 1 450 2. 42 05 +6 05 2 300 150 24 2:1 2 446 2. 26 02 +912 6. 5 300 150 24 1:0 1 2. 64 (Essentially the same as for Coatlng 5)300 150 24 1 0 2 2. 21 300 150 2:1 1 449 1. 94 05 0 04 2. 5 300 150 252:1 2 445 1. 76 04 0 05 5 300 150 25 1:0 1 2. 08 (Essentially the sameas for Coating 7) 300 150 25 1:0 2 1.84

The data show that my representative couplers used in the photographicelements produced good yellow dye images upon color developmentfollowing exposure to a light image.-D and A -values are good. Theyellow dye images have good stability to prolonged exposure to a highintensity light and good stability when stored under high temperatureand humidity conditions. The residual coupler in the-minimumdensity-areas of the processed emulsion layers exhibited a low amount ofprintout andyellowing. The data show that the coupler:coupler solventcan be used over a wide range, i.e., from 1:0 to 1:1 and that couplerssuch as 24 and 25 give good' reactivity even in the absence of the highboiling coupler solvent.

Similar results are obtained when my yellow-forming couplers areincorporated in amultilayer multicolor photographic element such as areused in color photography.

Example 2 A yellow color developer solution was prepared for each of myrepresentative difiusible couplers 19 and 20 yellow dye images thatfaded substantially less than the dye from the control coupler and whichwere equivalent or better for fading upon prolonged storage at elevatedtemperature and humidity.

Example 3 ,B-hydroxyethyl-v-stearamidopropyl ammonium dihydrogenphosphate, for three minutes at 75 F. After development the receivingsheets were separated from the respective coatings showing that theyellow dye images formed in the coatings were transferred to and weremordanted in the respective receiving sheets.

Example4 Singlelayer gelatin silver bromoiodide. coatings were preparedcontaining couplers 26, 28, 29, 31, 33, 35,36, and .40, respectively.Each of these couplers were dispersed in said coatings in the form of afinely dispersed solution of the coupler in coupler solvent,di-n-butylphthalate.

These coatings contained lOparts of gelatin, parts of silver, 2 parts ofcoupler, and 1 part of coupler solvent. Samples of the above mentionedcoatings were given second exposure on a 1B intensity scale sensitometerand processed in a conventional manner to color negatives, respectively,using the following developer solution:

Sodium sulfide (anhydrous) g 2.0 2-amino-5-diethylaminotoluene HCl g 2.0Sodium carbonate monohydrate 'g 20.0 Potassium bromide g 2.0 Water to 11.0 pH to 10.86.

.Each of the processed strips which contained the respective yellowcouplers contained high quality yellow dye images. The one stripcontaining the magenta dyeforming coupler 40 contained a high qualitymagenta dye image.

The preparation of my couplers is illustrated .by adescription ofrepresentative couplers of my invention.

Coupler 1 A mixture of 33 g. of a-pivalyl-u-chloro-4 sulfamylacetanilideand 40 g. of 4-nitro-3-pentadecylphenol sodium salt in 300 ml. ofacetonitrile was refluxed overnight, after which time the mixture wasfiltered and the filtrate was cooled to room temperature, whereupon asolid separated. The solid was collected and recrystallized four timesfrom acetonitrile, yielding 25 g. of coupler 1, M.P. 130-138 C.

- Coupler2 Intermediate No. l

a-Piv alyla- (4-nitrophenoxy -4-suliar'nylacetanilide A mixture of 16.7g. of a-pivalyl-a-chloro-4-sulfamylacetanilide, 7.7 .g. of 4-nitrophenoland. 5.4 g. of triethylamine in 150 ml. of acetonitrile was refluxedovernight, after which time the clear solution was concentrated invacuo. The residual oil was triturated with diethyl ether, whereupon itsolidified. This solid was recrystallized several times from ethanol,yielding g. of product.

Intermediate No. 2

a-Pivalyl-a-(4-aminophenoxy) -4-sulfamylacetanilide A mixture of 10.8 g.of Intermediate No. 1. and 150 ml. of ethyl alcohol was hydrogenated ina Parr hydrogenation apparatus at room temperature under a hydro genatmosphere of 30 p.s.i. using palladium on charcoal as the catalyst. Thetime required for the reduction was four hours, after which time thesolution was heated to boiling. Catalyst was removed by filtration andthe filtrate concentrated in vacuo. The solid residue was recrystallizedfrom methanol, yielding 4 g. of product.

1 4 Coupler 3 This coupler was prepared by the method used for coupler lexcepting that an equimolar amount ofa-pivalyl-achloro-2-chloro-4-sulfamylacetanilide was used in place ofa-pivalyl-a-chloro-4-sulfamylacetanilide. The recrystallized and driedcoupler had a M.P. of 116118 C.

Coupler 4 A mixture of 10 g. of 4-(N-rnethyl-N-octadecyl-sulfamyl)phenolsodium salt and 6.7 g. of a-pivayl-a-chloro- 4-sulfarnylacetanilide inml. of acetonitrile was refluxed overnight. The mixture was filtered andthe filtrate cooled in ice for several hours, whereupon a white solidseparated. This solid was collected and recrystallized from ethanol,yielding 3 g. of product, M.P. 991l1 C.

Coupler 5 This coupler was prepared by the method used for coupler 4excepting that .an equivalent amount of 4- methylsulfonylphenol sodiumsalt and a-pivalyl-a-chloro- 4-(N-methyl-N-octadecylsulfamyl)acetanilidewere used. The product had a M.P. of 82-89 C.

Coupler 6 This coupler was prepared by the method used for coupler 4 butsubstituting equivalent amounts of 4-sulfamylphenol sodium salt anda-pivalyl-a-chloro-4-(N- methyl-N-octadecylsulfamyl)acetanilide. Theproduct had a M.P. of 85-88 C.

Coupler 7 This coupler was prepared by the method used for coupler 4 butsubstituting equivalent amounts of 4-nitrophenol sodium salt andu-pivalyl-a-chloro-4-(N-methyl- N-octadecylsulfamyl)acetanilide. Thecoupler had a M.P. of 99101 C.

Coupler 8 A mixture of 12 g. of 4-nitro-3-pentadecylphenol sodium saltand 9 g. of a-benzoyl-a-chloro-2-methoxyacetanilide in 130 ml. ofacetonitrile was refluxed overnight, after which time the clear solutionwas cooled to room temperature, whereupon a solid separated. This solidwas collected and recrystallized twice from hexane, yielding 3 g. ofcoupler, M.P. 104106 C.

Coupler 9 A mixture of 4 g. of 4-nitrophenol sodium salt and 12.5 g. of(Jr-{3-[' -(2,4-di-tert-amylphenoxy)butyramido]benzoyl}-a-chloro-2-methoxyacetanilide in ml. of acetonitrile wasrefluxed overnight, after which time the mixture was filtered hot. Thefiltrate was cooled and concentrated in vacuo. The residual oil wastriturated with a diethyl ether-petroleum ether mixture, whereupon itsolidified. This solid was recrystallized twice from a 50:50 mixture ofhexane and ethylacetate and 3 times from acetonitrile, yielding 4 g. ofproduct, M.P. 153-160 C.

Coupler 10 This coupler was prepared by the method used to preparecoupler 9 but using an equivalent amount of 4- acetylphenol sodium saltin place of 4-nitrophenol sodium salt. The coupler had a M.P. of 142l48C.

Coupler 11 This coupler was prepared by the method used to preparecoupler 9 but using an equivalent amount of 4- sulfamylphenol sodiumsalt in place of 4-nitrophenol sodium salt. The coupler had a M.P. of193.5l97 C.

Coupler 12 This coupler was prepared like coupler 9 but using anequivalent amount of 4-phenylphenol sodium salt.

1 5 Coupler 13 This coupler was prepared by the method used to preparecoupler 8 but by using equivalent amounts of 4-(N-methyl-N-octadecylsulfamyl) phenol sodium salt and abenzoyl-a-chloro-2-ethoxyacetanilide. The coupler product had a M.P. of7377 C.

Coupler 14 A mixture of 1.5 g. of 4-methylsulfonylphenol, 1 g. oftriethylamine and 5.5 g. ofa(4-methoxybenzoyl)-a-chloro-S-[).-(2,4-di-tert-amylphenoxy)butyramido]-2chloroacetanilide in 40 ml. of acetonitrile was refluxed overnight,cooled and filtered to remove a small quantity of precipitate. Thefiltrate was concentrated in vacuo and the residue was recrystallizedthree times from ethanol, yielding 2 g. of product, M.P. 155-160 C.

Coupler 15 A mixture of 4 g. of the intermediate below and 1 g. ofsuccinic anhydride in 25 ml. of acetonitrile was stirred at roomtemperature overnight. The white solid which had separated from theclear reaction mixture was collected, washed with acetonitrile, anddried to yield 4.6 g. of product, M.P. 196-201 C.

Intermediate A1pha-( 4-aminophenoxy-alpha-pivalyl-4-(N,N-

dimethylsulfamyl) acetanilide A mixture of 14 g. ofalpha-(4-nitrophenoxy)-alpha pivalyl-4-(N,N-dimethylsulfamyl)acetanilideand a small amount of palladium on charcoal catalyst in 150 ml. ofp-dioxane was hydrogenated overnight at room temperature in a lowpressure Parr apparatus. The reaction mixture was filtered, and thefiltrate was concentrated in vacuo to yield a yellow gum. This residuewas triturated with methanol, whereupon a white crystalline solidseparated, was collected, washed with methanol, and dried to yield 11 g.of product.

Coupler 16 This coupler was prepared by the method used for coupler 1but using equivalent amounts of 4-r1itrophenol sodium salt and alphapivalyl-alpha-chlorol-(N,N-dimethylsulfamyl)acetanilide. The product hada M.P. of 195- 197 C.

Coupler 17 This coupler was prepared by the method used for coupler 8but using an equivalent amount of 4-nitrophenol sodium salt in place ofthe 4-nitro-3-pentadecylphenol sodium salt. The coupler product had aM.P. of 141- 157 C.

Coupler 18 To 20 ml. of dihydropyran was added 3 g. ofalphabenzoyl-alpha-hydroxyacetanilide, Intermediate No. 2, and one dropof concentrated hydrochloric acid with stirring. The resultant solutionbecame hot and reaction was allowed to take place with external heatingor cooling.

. .The clear solution was left at room temperature overnight.

.To the clear reaction mixture was then added hexane, whereupon a solidseparated, was filtered, and recrystallized twice from methanol,yielding 1 g. of product, M.P. ISO-131 C.

Intermediate No. l

Alpha-acetoxy-alpha-benzoylacetanilide A solution of 170 g. of alphabenzoyl-alpha-chloroacetanilide and 75 g. of anhydrous sodium acetate in1 liter of glacial acetic acid was refluxed overnight, after which time500 ml. of'water was added. The resultant solution was cooled, whereupona solid precipitated, was filtered and dried, yielding 150 g. ofproduct.

Intermediate No. 2

Alpha-benzoyl-alpha-hydroxyacetanilide Coupler 19 A mixture of 10.5 g.of 4-carbomethoxyphenol sodium salt and 15 g. ofalpha-benzoyl-alpha-chloro-2-methoxyacetanilide in 150 ml. ofacetonitrile was refluxed overnight, after which time it was filteredand concentrated in vacuo. The residual oil was triturated with diethylether', whereupon it solidified. The solid was recrystallized severaltimes from acetonitrile, yielding 3 g. of product, M.P. 146156 C. 1

Coupler 20 This coupler was prepared as Coupler 19, but using anequivalent amount of 4-sulfamylpheu0l sodium salt. The coupler had aM.P. of 191.5-196 C.

Coupler 21 A mixture of 14 g. ofalpha-benzoyl-alpha-(4-nitrophenoxy)-2-methoxyacetanilide and a smallamount of 10% palladium on charcoal catalyst in 200 ml. of pdioxane washydrogenated overnight at room temperature in a low pressure Parrapparatus. After this time, the reaction mixture was filtered and thefiltrate was concentrated to dryness in vacuo. The solid residue wasdissolved in diethyl ether at reflux. This ether solution was saturatedwith anhydrous hydrogen chloride gas, whereupon a solid separated. Thissolid was collected, washed with additional anhydrous ether, and driedto yield 15 g. of product, M.P. 122124 C.

Coupler 22 A mixture of 14 g. of 4-nitro-3-pentadecylphenol, 4.3 g. ofdiethylamine, 13.5 g. of alpha-pivalyl-alpha-chloro-4-fluorosulfonylacetanilide in 160 ml. of acetonitrile was refluxedovernight, after which time the clear solution was concentrated invacuo. The residual oil was dissolved in ml. of acetone. To thissolution was added a solution of 8 g. of potassium hydroxide in ml. ofwater. The resultant solution was refluxed for 30 minutes, after whichtime a solution of 10 ml. of acetic acid in 20 m1. of acetone was added,whereupon oil separated. This oil was triturated with ethanol and thesolution which formed was collected and recrystallized several timesfrom ethanol, yielding 2.3 g. of product.

Coupler 23 This coupler was prepared by reacting 4-(N-methyl-N-octadecylsulfamyl) phenol sodium salt andalpha-pivalylalpha-ch10ro-4-sulfoacetanilide, according to the procedureused for Coupler 4.

Coupler 24 A mixture of 6.7 g. of the intermediate below and 1 g. ofsuccinic anhydride in 25 ml. of acetonitrile was stirred at roomtemperature overnight. An additional 50 ml. of acetonitrile was addedand the mixture was warmed on a steam bath, whereupon a completesolution resulted. This solution was allowed to stir and cool to roomtemperature, during which time a solid separated. This solid wascollected and recrystallized once from acetonitrile to yield 7.4 g. ofproduct, M.P. 133-134 C.

.7 Intermediate Alpha-(4-aminophenoxy)-alpha-pivalyl-4-(N-methyl-N-octadecylsulfamyl -acetani1ide A mixture of 12 g. ofalpha-(4-nitrophenoxy)galphapivalyl-4-(N-methyl-N-octadecylsulfamyl)acetanilideand a small amount of palladium on charcoal catalyst in 200 ml. ofp-dioxane was hydrogenated at room temperature in a low pressure Parrapparatus for a period of 18 hours. The catalyst was removed byfiltration and the filtrate was concentrated to dryness in vacuo. Thesolid residue was recrystallized twice from acetonitrile and once frommethanol to yield 18 g. of product, M.P. 98-100 C.

Coupler This '-was prepared by reacting 4-sulfophenol sodium salt andalpha-pivalyl-alpha-chloro-4-(N-methyl-N-octadecylsulfamyl)acetanilide,according to the procedure used for Coupler 4.

Coupler 26 A mixture of 24 g. of alpha-chloro-alpha-pivalyl-(N-methyl-N-octadecylsulfamyl)acetanilide, 6 g. of meth'ylp-hydroxybenzoate, and 4 g. of triethylamine in 150 ml. of acetonitrilewas refluxed overnight with stirring, after which time it wasconcentrated in vacuo. The residue was recrystallized twice from methylalcohol to yield the product, M.P. 6970 C.

Coupler 27 Coupler 28 A mixture of 12 g. ofalpha-chloro-alpha-pivalyl-4- acetylacetanilideylS g. of4-(N-methyl-N-octadecylsulfamyl)-phenol, and 4 g. of triethylamine in120 ml; of acetonitrile was refluxed with stirring overnight, afterwhich time the mixture was concentrated in vacuo. The residue wasrecrystallized several times from methyl alcohol to yield the product,M.P. 798l C.

Coupler 29 A mixture of 12 g. of alpha-chloro-alphapivalyl-4-(N-methyl-N-octadecylsulfamyl)acetanilide, 10 g. of 4,4-sulfonyldiphenol, and 9 g. of triethylamine in 100 ml. of acetonitrilewas refluxed with stirring overnight, after which time the solution wasconcentrated in vacuo. The residue was recrystallized several times frommethyl alcohol to yield the product.

Coupler 30 A mixture of 12 g. of alpha-chloro-alpha-pivalyl-Z- chloro 5['y (2,4-di-t-amylphenoxy)butyramidolacetanilide, 4 g. of 4-hydroxybenzenesulfonic acid sodium salt, and 2 g. of triethylamine in 150 ml,of acetonitrile was refluxed with stirring overnight, after which timeit was concentrated in vacuo. The re idue was dissolved in 70 ml. ofabsolute ethyl alcohol and to this solution was added a solution of 6 g.of potassium acetate in 70 ml. of absolute ethyl alcohol. A small amountof solid which separated was removed by filtration and the filtrate wasagain concentrated in vacuo. The residue was dissolved with a mixture of120 ml. of ethyl alcohol and 40 ml. of water. A small amount ofinsoluble material was removed by filtration and the filtrate againconcentrated 18 in vacuo. The residue wastlien recrystallized fromacetonitrile to yield the product:

" I V Coupler 1 p ,A solution of 30, g. ofalpha chloro alpha;pivaly1*2-chloro -5- [7 (2,4-- di-t-arnylphenoxy)butyramidolacetanilide, 25v g. of4,4f-sulfonyldiphenol,-; and .20 lg. of triethylamine in 250 ml. ofacetonitrile was refluxed with stirring overnight, afterwhich time itwas concentrated in vacuo. The residue was dissolved in 300 ml. ofmethyl alcohol. The solution was poured' with -stirring into 1 liter ofice and water. The solid which separate was collected, dried, andtriturated several times with boiling hexaneto yield the'product, M.P.-99-101" C. T

' Coupler 32- A solution of 10 g. of alpha (4 carbobenzyloxyphenoxy):alpha pivalyl 3-(N-methyl-N-oetadecylsulf amyl)acetanilide in 100 ml.ofdioxane was reduced on the low pressure Parhydrogenationapparatus-using about /2 g. of palladium on charcoal asthepcatalystat 45 C. After the reduction was complete the catalyst wasremoved by filtration and the filtrate was concentrated in vacuo. Theresidue was recrystallized once from methanol and again fromacetonitrile to yield the product, M.P.

Coupler 33 V l M r A solution of 180 g. of alpha-chloro-alpha-pivalyl-4-(N methyl N octadecylsulfamyl)acetanilide, "69, g. of benzyl4-hydroxybenzoate, and '32 g. .of triethylamine in 1 liter ofacetonitrile was refluxed with stirring overnight, after which time itwas concentrated in vacuo. The residue was slurried in diethyl ether andthe insoluble triethylamine chloride was removed by filtration. Thefiltrate was chilled in an ice bath, whereupon a white solid separated,was collected and recrystallized from hexane toyield the product, M.P.8991 C.

Coupler 34 A solution of 87 g. of a-(4-carbobenzyloxyphenoxy)- a pivalyl2 chloro-5-[v-(2,4-di-t-amylphenoxy)butyramido]acetanilide in 400 ml. ofabsolute ethyl alcohol was reduced at room temperature on .the lowpressure Parr hydrogenation apparatus using 10% palladium on charcoalcatalyst. After the reduction was complete, the

catalyst was removed by filtration and the'filtrate concentrated invacuo. The residue was recrystallized from acetonitrile to yield theproduct, M.P. 193-194 C.

I Coupler 35 I A solution of 18 g. of ct-chloro-a-pivalyll-(N-methyl-N-octadecylsulfamyl)acetanilide, 5.5 g. of pentafiuorophenol, and 4.6 g.of triethylamine in ml. of acetonitrile was refluxed with stirringovernight, after which time it was concentrated in vacuo. The residuewas recrystallized 3 times from methyl alcohol to yield the product,M.P. 666 8 C.

I Coupler 36 This coupler was prepared in accordance with the procedureused for the preparation of Coupler 36 except thatalpha-benzoxyl-alpha-chloroacetanilide was used in place of the couple;intermediate used in the preparation of Coupler 36.

19 Coupler 38 This coupler was prepared in accordance with the procedureused to prepare Coupler 36 except thatalphachloro-alpha-pivalylacetanilide was used in place of the couplerintermediate of .Example ,36- and hydroquinone was .used in place of thephenol used in preparing Coupler 36.

' Couplers 39, 40, 41 and 43 Each of these couplers were prepared byreacting the alpha-chloro coupler. intermediate with the respectivephenols, ,using a procedure similar to that given for the preparation ofCoupler 1 The intermediates used in prepraing these couplers are givenin the following Table 3.

" 3 TABLE 3 Coupler Coupler Phenol Used No. 1 Intermediate 392-(alpha-chloro-alpha-cyanoacetyl)- -sulfamylphenol.

coumarone. 40 2-(alpha-chloro-alpha-cyanoacetyl)- -m'trophenol.

-14-(N-octadecylcarbamyl)phenylsullamyflcoumarone. 41Alpha-chloro-alpha-(Z-naphthoyl)- Phenol.

. acetanilide. 43.. Alpha-benzoyl-alpha-chloroacet- 4-hydroxypyr1dine.

anilide.

Coupler 42 To a solution of 2 g. of acetyl H-acid in 100 ml. of methylalcohol and about 50 ml. of crushed ice was added a methanolic solutionof the intermediate prepared below, together with a slight excess ofsodium acetate, with stirring. The red solid which separated wascollected and an additional second crop was obtained by partialevaporation of the reaction solution. The total solids were combined andslurried in water, triturated with dry petroleum ether, collected anddried to yield the product, M.P. decompose at 250 C.

Intermediate To a solution of 3.35 g. of alpha-(4-aminophenoxy)- alphapivalyl 4 (N methyl N octadecylsulfarmyD- acetanilide in 150 ml. ofn-propyl alcohol was added a mixture of 3 g. of p-toluene sulfonic acidand 5 ml. of acetic acid. To the resultant solution was added 3 g. ofisopentylnitrile. The reaction mixture was then stirred at roomtemperature overnight, after which time it was heated to 45 C. and thencooled to room temperature. The solvent was removed in vacuo and thegummy residue (i.e., the diazotized amine coupler) was used as such,without further purification, in the above reaction.

Coupler 43 This coupler was prepared by a method similar to that I usedto make Coupler 19 but using as the intermediates equimolar amounts of4-(N,N-dimethylsulfamyl)phenol sodium salt andalpha-benzoyl-alpha-chloro-2-decyloxyacetanilide. The coupler had a MP.of 89 C.

The chloroacetanilides used in the coupler syntheses were prepared asdescribed by McCrossen et al., US. Patents 2,728,658, issued Dec. 27,1955, and 2,875,057, issued Feb. 24, 1959, respectively, Loria, U.S.Ser. No. 247,302, filed Dec. 26, 1962, and Kibler and Weissberger, U.S.Ser. No. 364,450, filed May 4, 1964.

My two-equivalent dye-forming couplers are characterized from othercouplers by having a cyclooxy or a heterocyclooxy group attached to theactive carbon atom of the coupler molecule. My couplers are valuable foruse in color photography because of their relatively low printout, andyellowing in processed elements containing them, and because of thedesirable characteristics of the dyes produced from them, for examplelow heat fade, low light fade, good A D etc.

I The invention has been described in detail with particular referenceto preferred embodiments thereof but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention as described hereinabove and as defined in the appendedclaims.

1. An image-forming layer containing silver halide emulsion and acoupler which is capable of forming a dye on coupling with the oxidationproduct of an aromatic amino developing agent, said coupler containingfrom one to two open-chain reactive methylene groups, said methylenegroup being joined directly to two activating groups, at least one ofsaid activating groups being a carbonyl group, said active methylenegroup also being joined directly to a cyclooxy group selected from theclass consisting of a phenoxy group, a phenylenedioxy group, a naphthoxygroup, a naphthylenedioxy group, a pyridinyloxy group, a pyridyldioxygroup, a tetrahydropyranyloxy group, a tetrahydropyranylenedioxy group,a tetrahydroquinolyloxy group, and a tetrahydroquinolylenedioxy group,such that when the said coupler contains one open-chain reactivemethylene group the said cyclooxy group is monovalent and when the saidcoupler contains two reactive methylene groups the said cyclooxy groupis divalent, which cyclooxy group is eliminated on the coupling of saidcoupler with said oxidation products.

2. An image-forming layer containing silver halide emulsion and acoupler of the formula:

wherein n represents an integer of from 1 to 2; R represents a groupselected from the class consisting of an alkyl radical, an aryl radical,and a heterocyclic radical; R represents a group selected from the classconsisting of a carbamyl radical and a cyano radical; and R represents acyclo group selected from the class consisting of a phenyl group, aphenylene group, a naphthyl group, a naphthylene group, a pyridinylgroup, a pyridyl group, a tetrahydropyranyl group, atetrahydropyranylene group, a tetrahydroquinolinyl group and atetrahydroquinolylene group, such that when n represents the integer 1,R represents a monovalent cyclo group and when n represents the integer2, R represents a divalent cyclo group.

3. An image-forming layer containing silver halide emulsion and acoupler of the formula:

wherein R represents a group selected from the class consisting of analkyl radical, an aryl radical, and a heterocyclic radical; R representsa group selected from the class consisting of a carbamyl radical and acyano radical; R represents a cyclo group selected from the classconsisting of a phenyl group, a naphthyl group, a pyridinyl group, atetrahydropyranyl group and a tertahydroquinolyl group.

4. A light-sensitive hydrophilic colloid-silver halide emulsion layercontaining the coupler, alpha-{3-[v-(2,4- di tamylphenoxy)butyramido]benzoyl} alpha (4-nitrophenoxy-2-methoxyacetanilide.

5. A light-sensitive hydrophilic colloid-silver halide emulsion layercontaining the coupler, alpha-[4-(N- methyl N octadecylsulfamyl)phenoxy]alpha pivalyl- 4-sulfoacetanilide potassium salt.

6. A light-sensitive hydrophilic colloid-silver halide emulsion layercontaining the coupler, alpha-pivalylalpha (4 sulfophenoxy) 4 '(N methylN octadecylsulfamyl)acetanilide potassium salt.

7. A light sensitive hydrophilic colloid silver halide emulsion layercontaining the coupler, alpha-[4 (4- hydroxyphenylsulfonyl)phenoxy]alpha-pivalyl-Z-chloro- 5-[ 2,4-dit-amylphenoxy) butyramido]acetanilide.

21 22 8. A light-sensitive hydrophilic colloid-silver halide ReferencesCited emulsion layer containing the coupler, alpha-(4-carboxy- Pphenoxy) alpha pivalyl 2 chloro 5 ['y-(2,4-di-t- UNITED STTES ATENTSamylphenqxwbutyramido]acetanilide 3,227,550 1/1966 Wh1tmore et al. 9639. A light-sensitive hydrophilic colloid-silver halide 5 3,227,5511/1966 Barr et emulsion layer containing the coupler,4,4-bis[alphapivalyl alpha {2 cmoro 5 [7 (z,4 di t amylphenoxy) J.TRAVIS BROWN, Primary Examiner. butyramido] -phenylcarbamyl}methoxy]diphenylsulfone.

2 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. BIIOBJQL Dated October 29, 1968 Inventor(s) Anthony LOPiEl It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Cofiumn 19, line 51, delete m3", and substitute in its'place Column 20,line 58, delete the term terta-", and substitute in its place --tetr-a-SIGNED AND SEALED @EAL) Atteat:

Edward M- Fletcber, In mm E, ISGHUYLER, i1;- Attelting Officercommissioner Of Pabl'fl

